Preparing tetrachloroethylene



Feb. 20, 1934- J. H. REILLY 1,947,491

PREPARING TETRACHLOROETHYLENE Filed Feb. 1, 1933 2 Sheets-Sheet 1 E I i k k Q Q @4 E k. 9 3 Q i M k $1. s -s *Q I =,b W 6 s R w 8 N Q u u 3%, m afi E W *2 A (I) X") INVENTOR mg bhngzzeizg ATTORNEY Feb. 20, 1934.

J. H. REiLLY 1,947,491

PREPARING TETRACHLOROETHYLENE Filed Feb. 1, 1955 2 Sheets-Sheet 2 INVENTOR @7072 E fleilgy BY j Z I ATTORNEY Patented Feb. 20, 1934- UNI ED STATES 1.947.49i PREPARING reraacnroaonrmami;

John H. Reilly, Midland,

Mich assignor to The Dow Chemical Company, Midland, Mich, a corporation of Michigan mum... February 1. 1933. Serial Ni. 654.602

' 8 Claims. (c1. 260-166) The invention relates to pr for the preparation of tetrachloroethylene.

The preparation of tetrachloroethylene is ordinarily accomplished by chlorinating ethylene to pentachloroethane and reducing the pentachlorocompound with an alkali metal or alkaline earth metal hydroxide. In contrast to the foregoing. I have now found that tetrachloroethylene can be prepared directly in good yields by. the' treatment of an oleflne chloride with chlorine at temperatures between about300 and about 500 C. in the presence of a suitable catalytic agent.

The invention, then, consists of the steps hereinafter fully described and particularly pointed out in the claims, the annexed drawings and the following description setting forth in detail several modes ofcarrying out the invention, such disclosed modes illustrating, however, but several of various ways in which the principle of the invention may be used.

In said annexeddrawingsz- Figure 1 shows tically in side elevation suitable apparatus for carrying out my invention.

Figure 2 is a side elevation, partially in section, of the reactor shown in Figure l.

Figure 3 is a sectional elevation of the-reactor 'inFi'gureiitakenonthelineH.

My improved process for the preparation of tetrachloroetlrvlene comprises passing a mixture of an oleflne chloride and chlorine, in the gaseous phase, through a reactor packed with a porous surface catalyst and maintained at a temperature of 300 to 500 (2., and condensing 1581180111010!- ethylene'from the reaction'product. Among the porous surface catalysts suitable for use in my process are coke, charcoal, pumice, alundum, silica gel and metallic oxidegels generally, unglazed porcelain,- etc. when oleflne chlorides higher in the seriesthan ethylene chloride are treated in the foregoing manner,- carbon tetrachloride is produced concurrently with the'tetrachloroethylene. v

I The following Equations (1) and (2) illustrate the reaction by which'tetrachloroethylene is ob-' tainedfrom ethylene chloride and. P p lene chloride, reapectivelyfliy my process, and Equation (2) shows the concurrent product of carbon (1) CzHaCls-l-W-I-HCI (2i CilioCla+0Clr CsGk+OOh+8HCi I can use olefine "chlorides, such'ias butyleiie and amylenechlorideinmyprocesabutflieyieidsof.

when the lower members of the series are used since more carbon tetrachloride is produced. The foregoing reactions are exothermic in character and I have found that by exercising proper control it ,ispossible to carry out the process without an. supplying any additional heat beyond that generated by the reaction.

.To produce a mixture of an oleflne chloride and chlorine suitable for passing into the reactor I have found it convenient to preheat the olefine 5 chloride to a temperature between about 120 and 180 C. before admixing the chlorine therewith. Highly purified chlorine is not essential for use in my process, in fact, I have successfully used chlorine containing up to 20 per cent of air. 7 The type oi vessel in which the mixture of oleflne chloride and chlorine may be reacted is capable of considerable variation as regards structure: but I have found that a reactor containing a plurality of small tubes, say about one inch inside 1 diameter, through which the reactants are passed, may be used advantageously.

The. tubes of the reactor are filled. ith a suitablyscreen'ed and sized porous surface catalyst. One of the functions a: such catalyst is to pre-'-- vent the propagation of flame in the reactor tubes, such as would occur if the tubes were empty; To assist in the proper control of the exothermic reaction within the tubes I have foundthat by circulating therearound a suitable heat a transfer fluid that the te rature can be controlled within narrow limits. The heat transfer fluid stabilizes the temperature by supplying heat I to the reactants when the reaction rate falls, and by extracting heat therefrom when the reaction becomes too rapid, The temperature of the reaction can be controlled within narrow limits in such a reactor resulting in better yields of tetra- .chloroethylene.

The heat transfer fluid, if liquid, should have a boiling point between about 300 and 500 "C. Among the suitable substances which I may use are chlorinateddiphenyloxi'des, diphenylbenzene,

sodium nitrite,-metallic sodium, mercury, high velocity recirculated gas, such as air or stack too.-

gases, etc. v

The condensation from the reaction products of the tetrachloroethylene, and carbon tetrachloride when such is. aproduct, may be effected.

I in any suitable way. For example, by spraying 106 water directlyinto the and layering-o! the resulting condensate. The condensation may also be effected in a coil or plate-type condenser,

pure tetrachloroethylene canbe obtained 1 from thepondensatauponone distillation. it.

) Referring now to Figure 1, an oleflne is introduced through pipe 1 into a preheater and vaporizer 2, shown here as double pipe coil, with steam circulated through the outer coil to g heatthe oleflne chloride. The vapors of oleflne chloride pass from the preheater through a pipe 3 into a mixing. chamber 4. Chlorine is admitted to the mixing chamber through a pipe 5 and the mixture of gases then a: into the reactor 6,

shownin detail in Figures 2 and}.

The reactor consists of an inner shell 7 having a flanged opening at either end. The openingsare ciosedbyaflangedinletcapaanda similar outlet cap 9. A bundle of tubes 10 is containedwithinthereactorlnnershell'l. The tubes are held in place by a tube sheet at either end. designated at the outlet end by the numeral 11. The tube sheets are interposed between the inner shell flanges and thecap flanges to form a cation between the chamber 12 surrounding the tubes lorand the chambers 13 in the inlet and outlet caps. The tubes 10 and chambers 13 are ,packed with a porous surface catalytic agent 14. gs The chamber 12 within the reactor: inner shell 7 contains a heat transfer fluid 15. This heat transfer fluid may be partially vaporized during operation, in which case the vapors rise into the reflux condenser 16. Gas burners l7 are'provida ed to supply such heat to the reaction chamber ucts of combusthe Jacket 18 escape through as may be necessary. The pr A tion from the burners pass thro around the reactor shell I and the stack 19.

as The products of reaction leave the reactor through a pipe 20 and pass into a'condenser 21. The crude liquor condensed therein is drawn oi! to a storage 22 from which it may be withdrawn as desired for distillation to recover substantially pure" tetrachloroethylene therefrom. The uncondensed gases pass from the condenser into a scrubber tower 23 which remom by a water spray the hydrogen chloride contained therein.

vention in apparatus as hereinbefore described is as follows:-Ethylene chloride was passed into the preheaterand the temperature thereofraised to about 150' C., whereupon it was mixed with approximately twicedtsvweight of chlorine and g5 longerhave resulted in yields of tetrachloroethyleneaveragingabout'lopercentbasedonthe amount of ethylene chloride fed into the reactor.

Crude liquor resulting from carrying out the foregoing process was subjected to distillation V 10 with the following resuitsz-A 750 cc. sample began to boil at C. and from that temperature to 119 C. 97.5 0! distillate was collected. At exactly 11$,C. there was obtained 600 milliliters of tetrschloroethylene. when the 75 temperaturestartedtoriseabove 119C.thediefluid-tight joint, thereby preventing communi-- An example illustrating the practice of my in chloridetillation was stopped. The residue, 52s 'mmiliters, was substantially hexachloroethane. 'nus shows approximately per cent of the crude llqnor was substantially pure tetrachloroethylene.

when using propylene chloride as the oleflne chloride, I have obtained a crude liquor containing approximately 20 percent by volume of carbon tetrachloride and 55 per cent by volumeof tetrachloroethylene. The temperature conditions under which the conversion was carried out were approximately the same as when using ethylene chloride as raw material.

Among the advantagm which inure to my novel process for the preparation of tetrachloroethylene from oieflne chlorides are:--(1) a very high percentage ,of the oleflne chloride is converted to tetrachloroethylene; and. (2) the thermal emciency of the process is extremely high because the heat'required is supplied by the reaction.

Other modes of apv r s the principle of my invention may be employed instead of those explained, change being made as regards'the'processhereindisclosedprovidedthesteporsteps statedbyany'ofthefollowingclaimsorthe equivalentofsuchstatedsteporstepsbea'n- Dloyed.

Ithereforeparticularlypointoutanddistinctiy claim as my invention:-

1. In preparing tetrachloroethylene, the step whichconsistsinsubiectingamixmreofanolefine chloride and chlorine to a temperature between about 300' and about 500 C. in the prese'nce of a porous surface catalyst.

2. In preparing tetrachlo'roethylene, the steps which consist in subjecting a mixture of an ole-r flne chloride and chlorine to a temperature between about 300' and about 500' C. in the presence of a porous surface catalyst,cooling the reaction products, and separating therefrom. 1 3. In preparing tetrachloroethylene, the steps which consistin preheating an oleflne chloride tovaporizethesamemixingtherewithchlorine. subiectingthemlxtureofgastoatemperature betweenabout30o'andabout50o'CJnthepresenceofaporoussurfacecatalystcoolingtbere tetrachlou'oaction products, 'and separating ethylenetherefrom.

4. In preparing tetrachlorathylenefthe steps whichconsistinpreheatinganoleflneehloride to atemperature between about 120. and about C mixing therewith chlorine, passing the soformed mixtureof gases intoareactionsone containing a porous surface catalystandmaintained at a temperature between about 300' 1 andaboutwo'cscoolingthereaction and separating tetraohloroetbyiene-there'from.

5. In preparing tetrachloroethyiene. the steps which consist in preheating an oleflne chloride, mixing therewith chlorinejpaleing the soformed mixture into a reaction chamber maintained at a temperature between about 300 and about 500 C. containingaporoussurface catalystandsurroundedby a heat transfer fluid, reaction products. and separating tetrachloro- ;i

s. In preparing'tetrachloroethylene, the steps which consist in preheating an oleflne chloride higher in the series than ethylene chloride. mixing therewith chlorine, passing the so formed 34 mixtureintoareactlonchambermaintainedata temperature between about 300' andabout 500' C. containing aporoussurfacecatalystandsurroundedbysheattransferflmcoolhmtbere-' action prodmtsjand distilling he R M tog'li and tetrachlorowhich consist in preheating ethylene chloride to a temperature of about 150 C., mixing therewith chlorine, passing the so formed mixture into a reaction chamber maintained at a temperature of about 375 C., packed with a porous surface catalyst and surrounded with a heat'transfer fluid, cooling the reaction products to about room temperature, and distilling the liquid products to separate tetrachloroethylene' therefrom. v

JOHN H. REILLY. 

